U.S. patent number 5,844,053 [Application Number 08/737,253] was granted by the patent office on 1998-12-01 for organo-polysiloxane derivartives.
This patent grant is currently assigned to Nagase-Ciba, Ltd.. Invention is credited to Hirofumi Nishida.
United States Patent |
5,844,053 |
Nishida |
December 1, 1998 |
**Please see images for:
( Certificate of Correction ) ** |
Organo-polysiloxane derivartives
Abstract
The disclosed organo-polysiloxane derivative is useful as a
dispersing agent for homogeneously dispersing a silicone gel in a
curable resin such as an epoxy resin. The organo-polysiloxane
derivative is prepared by first reacting an organo-polysiloxane
compound A having an active hydrogen-containing group in each of
its both terminals and having from 5 to 70 siloxane bonds with a
bifunctional organic compound B having two functional groups
reactable with active hydrogen. The reaction mixture obtained in
the first reaction is reacted with a mixture of a bifunctional
organic compound C having two active hydrogens and a bifunctional
organic compound D having two functional groups reactable with the
active hydrogen.
Inventors: |
Nishida; Hirofumi (Himeji,
JP) |
Assignee: |
Nagase-Ciba, Ltd.
(JP)
|
Family
ID: |
13753020 |
Appl.
No.: |
08/737,253 |
Filed: |
October 29, 1996 |
PCT
Filed: |
March 14, 1996 |
PCT No.: |
PCT/JP96/00649 |
371
Date: |
October 29, 1996 |
102(e)
Date: |
October 29, 1996 |
PCT
Pub. No.: |
WO96/28496 |
PCT
Pub. Date: |
September 19, 1996 |
Foreign Application Priority Data
|
|
|
|
|
Mar 14, 1995 [JP] |
|
|
7-081678 |
|
Current U.S.
Class: |
525/476; 528/25;
528/27; 528/29; 528/30; 528/28; 528/26 |
Current CPC
Class: |
C08L
63/00 (20130101); C08G 18/61 (20130101); C08L
83/04 (20130101); C08G 18/10 (20130101); C08G
18/10 (20130101); C08G 18/3206 (20130101); C08G
18/10 (20130101); C08G 18/72 (20130101); C08L
63/00 (20130101); C08L 83/00 (20130101); C08L
83/04 (20130101); C08L 2666/14 (20130101); C08G
77/14 (20130101); C08G 77/26 (20130101); C08G
77/12 (20130101); C08G 77/42 (20130101); C08G
77/16 (20130101); C08G 2220/00 (20130101); C08G
77/28 (20130101) |
Current International
Class: |
C08L
83/00 (20060101); C08L 63/00 (20060101); C08G
18/10 (20060101); C08G 18/61 (20060101); C08L
83/04 (20060101); C08G 18/00 (20060101); C08F
283/00 () |
Field of
Search: |
;525/476
;528/25,26,27,28,29,30 |
References Cited
[Referenced By]
U.S. Patent Documents
Foreign Patent Documents
|
|
|
|
|
|
|
4292676 |
|
Oct 1992 |
|
JP |
|
665375 |
|
Mar 1994 |
|
JP |
|
61185527 |
|
Aug 1996 |
|
JP |
|
Primary Examiner: Marquis; Melvyn I.
Attorney, Agent or Firm: Lorusso & Loud
Claims
I claim:
1. An organo-polysiloxane having repeating units of a structure
represented by the formula: ##STR26## wherein A is the residue of
an organo-polysiloxane compound containing the unit: ##STR27##
wherein X and Y are each a hydrocarbon group or a halogenated
hydrocarbon group, t is an integer of from 5 to 90 and f is zero or
1, and having active hydrogen terminal groups selected from the
group consisting of --OH, --COOH, and --SH and connected to a
terminal silicon atom through a divalent aliphatic, aromatic or
heterocyclic connecting group;
B is the residue of a bifunctional organic compound of the formula
L--R.sup.4 --L wherein L is a functional group reactive with said
active hydrogen terminal groups and R.sup.4 is a divalent aromatic
group selected from the group consisting of:
(i) --Ar--,
(ii) --R--Ar--R--,
(iii) --RO--Ar--OR--, and
(iv) --CH.sub.2 --.sub.m-1 --OArOCH.sub.2 --
wherein R is a lower alkylene group having from 1 to 6 carbon
atoms;
Ar is a divalent aromatic group;
C is the residue of a bifunctional organic compound having two
active hydrogen-containing groups; and
D is the residue of a bifunctional organic compound having two
active functional groups reactive with said active
hydrogen-containing groups; and wherein:
m denotes an integer of 1 or 2; and
p denotes an integer of from 1 to 20.
2. An organo-polysiloxane derivative as claimed in claim 1, where B
and D are the same.
3. An organo-polysiloxane derivative as claimed in claim 1 wherein
t is an integer of 20 to 50.
4. An organo-polysiloxane derivative as claimed in claim 1 and
wherein t is an integer of 35 to 40 and f is zero.
5. A curable resin composition comprising an organo-polysiloxane
derivative as claimed in claim 1 and a silicone gel.
6. An organo-polysiloxane having repeating units of a structure
represented by the formula:
wherein:
A is the residue of an organo-polysiloxane compound containing 5 to
90 repeating units of the structure: ##STR28## wherein X and Y are
each a hydrocarbon group or a halogenated hydrocarbon group, t is
an integer of from 5 to 90 and f is zero or 1, and having active
hydrogen terminal groups selected from the group consisting of
--OH, --COOH, and --SH and connected to a terminal silicon atom
through a divalent aliphatic, aromatic or heterocyclic connecting
group;
B is a residue of a bifunctional aromatic epoxy compound of the
formula: ##STR29## wherein Ar.sup.1 is a divalent aromatic group;
and m is an integer of 1 or 2;
C is a residue of a divalent phenol compound of the formula:
wherein Ar.sup.2 is a divalent aromatic group;
m is an integer of 1 or 2 ; and
p is an integer of from 1 to 20.
7. A curable resin composition comprising an organo-polysiloxane
derivative as claimed in claim 6 and a silicone gel.
8. A process for preparing an organo-polysiloxane derivative
comprising:
reacting an organo-polysiloxane compound A having an active
hydrogen terminal group at each of its terminal ends with a
bifunctional organic compound B having two functional groups which
are reactive with said active hydrogen terminal groups to produce
an intermediate reaction mixture and then reacting the intermediate
reaction mixture with a mixture of a bifunctional organic compound
C having two active hydrogen-containing groups and a bifunctional
organic compound D having two functional groups each reactive with
said active hydrogen-containing groups, wherein:
A is an organo-polysiloxane compound containing 5 to 90 repeating
units of the structure: ##STR30## wherein X and Y are each a
hydrocarbon group or a halogenated hydrocarbon group, t is an
integer of from 5 to 90 and f is zero or 1, and wherein each of its
terminal groups is selected from the group consisting of --OH,
--COOH, and --SH and connected to a terminal silicon atom through a
divalent aliphatic, aromatic or heterocyclic connecting group;
B is a bifunctional organic compound of the formula L--R.sup.4 --L
wherein L is a functional group reactive with said terminal groups
and R.sup.4 is a divalent aromatic group selected from the group
consisting of:
(i) --Ar--,
(ii) --R--Ar--R--,
(iii) --RO--Ar--OR--, and
(iv) --CH.sub.2 --.sub.m-1 --OArOCH.sub.2 --
wherein R is a lower alkylene group having from 1 to 6 carbon atoms
and Ar is a divalent aromatic group;
to produce the organo-polysiloxane derivative having a structure
represented by the formula: ##STR31## wherein A', B', C' and D' are
residues of the compounds A, B, C and D, respectively;
m is an integer of 1 or 2; and
p is an integer of from 1-20.
9. A process for preparing an organo-polysiloxane derivative as
claimed in claim 8, wherein B and D are the same compound.
10. A process for preparing an organo-polysiloxane derivative
comprising:
reacting an organo-polysiloxane compound A having an active
hydrogen terminal group at both of its terminal ends with a
bifunctional aromatic epoxy compound which yields the residue B and
has two functional groups which are reactive with said terminal
groups to produce an intermediate reaction mixture and then
reacting the intermediate reaction mixture with a mixture of said
bifunctional aromatic epoxy compound and a divalent phenol compound
which yields the residue C, wherein:
A is an organo-polysiloxane compound containing 5 to 90 repeating
units of the structure: ##STR32## wherein X and Y are each a
hydrocarbon group or a halogenated hydrocarbon group, t is an
integer of from 5 to 90 and f is zero or 1, and having active
hydrogen terminal groups selected from the group consisting of
--OH, --COOH, and --SH and connected to a terminal silicon atom
through a divalent aliphatic, aromatic or heterocyclic connecting
group;
B is a residue of a bifunctional aromatic epoxy compound which the
formula: ##STR33## wherein Ar.sup.1 is a divalent aromatic group;
and m is an integer of 1 or 2;
C is a residue of a divalent phenol compound with the formula:
wherein Ar.sup.2 is a divalent aromatic group;
to produce the organo-polysiloxane derivative having a structure
represented by the formula: ##STR34## wherein: A' is the residue of
the compound A; n is an integer of from 1-20; and
p is an integer of from 1-20.
Description
TECHNICAL BACKGROUND
The present invention relates to an organo-polysiloxane derivative,
a process for the preparation thereof, a dispersing agent for
dispersing a silicone gel in a curable resin, and a curable resin
composition containing the dispersing agent and the silicone
gel.
BACKGROUND ART
Epoxy resins are so superior in thermal, mechanical an electrical
characteristics that they hitherto have been utilized extensively
as adhesives, paints, materials for insulating electrical and
electronic parts, materials for sealing electrical and electronic
parts, and so on.
For epoxy resins, however, cured articles obtained by curing the
epoxy resins present the problem that internal stress may be caused
to occur in the cured articles, resulting various problems. For
instance, in instances where electronic parts are sealed with an
epoxy resin the cured epoxy resin may cause trouble or damage in
the electrical and electronic parts sealed by the epoxy resin due
to its internal stress.
It has been proposed that silicone gel be added in order to
decrease the internal stress of the cured epoxy resin articles
(Japanese Patent Unexamined Publication No. 61-185,527). The
silicone gel, however, suffers from the disadvantage that it is
difficult to disperse in an epoxy resin because it is poor in
compatibility with the epoxy resin.
Further, generally speaking, although not limited to the curable
epoxy resins, curable resins are likely to cause internal stress
when cured. For the curable resins other than the epoxy resins, it
is also possible to decrease the internal stress in their cured
materials by adding a silicone gel thereto. It has been found
difficult, however, to disperse the silicone gel in the curable
resins other than the epoxy resins.
The objects of the present invention include the following
(1) To provide an organo-polysiloxane derivative useful as a
dispersing agent for dispersing a silicone gel in a curable resin
homogeneously and a process for the preparation thereof;
(2) To provide a dispersing agent for a silicone gel for dispersing
the silicone gel in a curable resin homogeneously; and
(3) To provide a curable resin composition containing the silicone
gel and the dispersing agent for the silicone gel.
Other objects of the present invention will be understood by the
description that follows.
DISCLOSURE OF INVENTION
The present invention provides:
(1) An organo-polysiloxane derivative characterized by having a
chemical structure as represented by general formula (1) below in
its moiety;
(2) A process for the preparation of the organo-polysiloxane
derivative having the chemical structure as represented by general
formula (1) below in its moiety, which is characterized by the
first reaction step in which an organo-polysiloxane compound A
having an active hydrogen-containing group at each of its terminal
and having from 5 to 70 siloxane bonds is reacted with a
bifunctional organic compound B having two functional groups each
reactable with the active hydrogen thereof and by the reaction of
the reaction product obtained by the first step with a mixture of a
bifunctional organic compound C having two active
hydrogen-containing groups with a bifunctional organic compound D
having two functional groups each reactable with the active
hydrogen;
(3) A dispersing agent for dispersing the silicone gel in a curable
resin, characterized by the organo-polysiloxane derivative having
the chemical structure as represented by general formula (1) below
in its moiety; and
(4) A curable resin composition characterized by containing the
silicone gel and the organo-polysiloxane derivative having the
chemical structure as represented by general formula (1) below in
its moiety.
In the general formula (1),
A denotes the organo-polysiloxane compound A;
B denotes the bifunctional organic compound B;
C denotes the bifunctional organic compound C;
D denotes the bifunctional organic compound D;
n denotes an integer of from 1 to 20, preferably from 1 to 14;
and
p denotes an integer of from 1 to 20, preferably from 1 to 17.
It is to be noted that the bifunctional organic compound B may be
the same as the bifunctional organic compound D. In this case, the
general formula (1) may be rewritten as general formula (2) as
follows:
In accordance with the present invention, the organo-polysiloxane
derivative having the chemical structure as represented by general
formula (1) can be prepared by the two reaction steps as will be
described by the reaction formulas as follows:
(First reaction step)
(Second reaction step)
In the above general formulas, reference symbols A, B, C, D, n and
p have the same meanings as above.
In the organo-polysiloxane compound A to be employed as a raw
material in the present invention, the groups containing active
hydrogen connected to both terminals may include a hydroxyl group
(--OH), a carboxyl group (--COOH), a mercapto group (--SH), an
amino group (--NH.sub.2), --NHR (where R=a substituent), an amide
group (--CONH.sub.2) and so on. These active hydrogen-containing
groups are connected to the silicone atom (Si) through a connection
group. As the connection group in this case, there may be mentioned
a divalent aliphatic group, aromatic group or heterocyclic group.
In the carbon chain of the aliphatic group, there may be contained
a hetero atom such as an oxygen atom, a nitrogen atom, a sulfur
atom or the like.
The divalent aliphatic group may be a linear or cyclic alkylene
group. As the linear alkylene group, there may be mentioned, for
example, an alkylene group having from 1 to 20 carbon atoms, such
as, e.g. methylene, ethylene, propylene, butylene, hexylene,
octylene, dodecylene, hexadecylene, octadecylene or the like. As
the cyclic alkylene (cycloalkylene) group, there may be mentioned,
for example, cyclopropylene, cyclobutylene, cyclopentylene,
cyclohexylene, cyclohexenylene or the like. These linear or cyclic
alkylene groups may contain a double bond. Further, the divalent
aliphatic group may include an oxyalkylene group or a
polyoxyalkylene group, as represented by general formula
--(RO).sub.s -- (where reference symbol R denotes a lower alkylene
group such as ethylene, propylene, butylene or the like; and
reference symbol s denotes an integer of from 1 to 20, preferably
from 2 to 10).
As the divalent aromatic group, there may be mentioned, for
example, a divalent aromatic group derived from an aromatic
compound such as benzene, toluene, xylene, ethylbenzene,
methoxybenzene, methoxydiphenyl, cyanobenzene, nitrobenzene,
cumene, bisphenylmethane, bisphenylpropane, biphenyl, naphthalene,
phenanthrene and the like. As the divalent heterocyclic group,
there may be mentioned, for example, a divalent heterocyclic group
derived from furan, tetrahydrofuran, pyrrole, thiophene,
benzofuran, carbazole, pyridine, piperidine, pyran and quinoline
and a derivative thereof with its nucleus provided with a
substituent.
The polysiloxane bond may be represented by general formula (5) as
follows: ##STR1##
In the above formula, reference symbols X and Y may be a
hydrocarbon group or a halogenated hydrocarbon group and one of
them may be hydrogen. Reference symbol t may be an integer of from
5 to 90, preferably from 20 to 50, more preferably from 35 to 40,
and reference symbol f may be zero or 1 although it is zero in
usual case.
As the hydrocarbon group, there may be mentioned, for example, a
lower alkyl group having from 1 to 6 carbon atoms such as methyl,
ethyl, propyl, butyl, hexyl or the like; an aryl group such as
phenyl, tolyl or the like; a lower alkenyl group such as vinyl,
allyl, propenyl or the like; an aralkyl group such as benzyl,
phenethyl or the like; and a cycloalkyl group such as cyclopentyl,
cyclohexyl or the like. As the halogenated hydrocarbon group, there
may be mentioned, for example, tetrafluoroethyl, perfluorovinyl,
dichlorophenyl, trifluorophenyl, and so on.
In the general formula (5) above, reference symbols X and Y may
preferably be methyl group or phenyl group. It is preferred that
reference symbol t is set within the scope as defined hereinabove.
If it is set larger than the above-defined upper value, on the one
hand, it is less preferred because operability of the
organo-polysiloxane derivative may become diminished when it is
employed as a dispersing agent and, if it is set smaller than the
above-defined lower value, on the other hand, it is less preferred
because dispersibility of a silicone gel in the curable resin may
become lesser.
Some specific examples of the organo-polysiloxane compounds as
described hereinabove may be illustrated as follows: ##STR2##
In the above general formula, reference symbol R.sup.1 denotes
methyl group or phenyl group; reference symbol Z denotes --OH,
--COOH, --NH.sub.2 or --SH; reference symbol R.sub.2 denotes a
lower alkylene group; reference symbol t denotes an integer of from
5 to 90, preferably from 20 to 50, more preferably from 35 to 40:
##STR3## In the above general formula, reference symbol Z denotes
--COOH, --NH.sub.2 or --SH; and reference symbols R.sup.1, R.sup.2
and t have the same meanings as above: ##STR4## In the above
general formula, reference symbol Z denotes --COOH, --NH.sub.2 or
--SH; reference symbol R.sup.3 denotes ethylene group or propylene
group; reference symbol q denotes an integer of from 1 to 20,
preferably from 2 to 10; and reference symbols R.sup.1 and t have
the same meanings as above.
A variety of the organo-polysiloxane compounds having an active
hydrogen-containing group at each of its both terminals may be
commercially available. Some of such organo-polysiloxane compounds
may be enumerated as follows: For example, trade name "BY16-853"
(amino groups at both terminals; amino equivalent: 650), trade name
"BY16-853B" (amino groups at both terminals; amino equivalent:
2,200), trade name "BY16-752" (hydroxyphenyl groups at both
terminals; OH equivalent: 1,574), trade name "BY16-150B"
(hydroxyphenyl groups at both terminals; OH equivalent: 4,500),
trade name "BY16-150C" (hydroxyphenyl groups at both terminals; OH
equivalent: 10,000), and trade name "BY16-750" (carboxyl groups at
both terminals; carboxyl equivalent: 700), each prepared by
Toray-Dow Corning Silicone K.K.; trade name "TSL 9346" (amino
groups at both terminals; amino equivalent: 250), trade name "TSL
9386" (amino groups at both terminals; amino equivalent: 400),
trade name "TSL 9836" (mercapto groups at both terminals; SH
equivalent: 260), trade name "TSL 9876" (mercapto groups at both
terminals; SH equivalent: 410), trade name "TSL 9846" (mercapto
groups at both terminals; SH equivalent: 290), and trade name "TSL
9886" (mercapto groups at both terminals; SH equivalent: 440), each
prepared by Toshiba Silicone K.K.; trade name "X-22-161AS" (amino
groups at both terminals; amino equivalent: 450), trade name
"X-22-161A" (amino groups at both terminals; amino equivalent:
840), trade name "X-22-161B" (amino groups at both terminals; amino
equivalent: 1,500), trade name "X-22-161C" (amino groups at both
terminals; amino equivalent: 2,300), trade name "X-22-162A"
(carboxyl groups at both terminals; carboxyl equivalent: 2,330),
trade name "X-22-162C" (carboxyl groups at both terminals; carboxyl
equivalent: 920), trade name "X-22-167B" (mercapto groups at both
terminals; SH equivalent: 1,670), and trade name "X-22-165B"
(hydroxyphenyl groups at both terminals; OH equivalent: 2,000),
each prepared by Shin-Etsu Silicone K.K.; trade name "F-204-51"
(amino groups at both terminals; amino equivalent: 1,000), and
trade name "F-204-52" (amino groups at both terminals; amino
equivalent: 3,700), each prepared by Nippon Unicar K.K.
The bifunctional organic compound B having two functional groups
reactable with the active hydrogen may be an aliphatic compound, an
aromatic compound or a heterocyclic compound. The bifunctional
organic compound B may be represented by general formula as
follows:
In the general formula as described hereinabove, reference symbol
R.sup.4 denotes a divalent organic group; reference symbol L
denotes a functional group reactable with active hydrogen; and
R.sup.4 denotes a substituent having no active hydrogen, such as an
alkoxy group, an alkoxycarbonyl group, an acyl group, a nitro
group, a cyano group, and a halogen group.
The divalent organic group R.sup.4 may be a divalent aliphatic
group, a divalent aromatic group or a divalent heterocyclic
group.
The divalent aliphatic group may be a linear or cyclic alkylene
group. As the linear alkylene group, there may be mentioned an
alkylene group having from 1 to 20, preferably from 1 to 10 carbon
atoms. As the cyclic alkylene (cycloalkylene) group, there may be
mentioned cyclopropylene, cyclobutylene, cyclopentylene,
cyclohexylene, cyclohexenylene and so on. These linear or cyclic
alkylene groups may contain a double bond. Further, the divalent
aliphatic group may contain a hetero atom, such as oxygen,
nitrogen, sulfur or the like, in its carbon chain.
The divalent aromatic group may be represented by the following
general formula to be derived from a variety of aromatic
compounds:
(i) --Ar--
where reference symbol Ar denotes a divalent aromatic group derived
from aromatic compounds such as benzene, toluene, xylene,
ethylbenzene, methoxybenzene, methoxydiphenyl, cyanobenzene,
nitrobenzene, cumene, bisphenylmethane, bisphenylpropane, biphenyl,
naphthalene, phenanthrene and so on;
(ii) --R--Ar--R--
where reference symbol Ar denotes the divalent aromatic group and
reference symbol R denotes a lower alkylene group having from 1 to
6 carbon atoms;
(iii) --RO--Ar--OR--
where reference symbol Ar denotes the divalent aromatic group and
reference symbol R denotes the lower alkylene group; and
(iv) --CH.sub.2 --[OArOCHOHCH.sub.2 ].sub.m-1 --OArOCH.sub.2
--.
where reference symbol Ar denotes the divalent aromatic group and
reference symbol m denotes an integer of 1 or 2.
As the divalent heterocyclic group, there may be mentioned a
divalent heterocyclic group derived from furan, tetrahydrofuran,
pyrrole, thiophene, benzofuran, carbazole, pyridine, piperidine,
pyran, quinoline or a derivative having its nucleus
substituted.
As the functional group L in the general formula (9) above, there
may be mentioned epoxy group, isocyanato group (--NCO), carboxyl
group, an ester group, hydroxyl group, a halogen atom and so
on.
Some specific examples of the bifunctional organic compounds B may
be enumerated as follows:
(i) ##STR5## where reference symbol R denotes the divalent
aliphatic group, the divalent aromatic group or the divalent
heterocyclic group and reference symbol m is an integer of 1 or
2;
(ii) OCN--R.sup.4 --NCO
where reference symbol R.sup.4 denotes the divalent aliphatic
group, the divalent aromatic group or the divalent heterocyclic
group;
(iii) HOOC--R--COOH
where reference symbol R.sup.4 denotes the divalent aliphatic
group, the divalent aromatic group or the divalent heterocyclic
group;
(iv) ##STR6## where reference symbol R denotes an aromatic group,
such as phenyl group, tolyl group or the like, or a lower alkyl
group such as methyl group, ethyl group or the like; and
(v) ROOC--R.sup.4 --COOR
where reference symbol R.sup.4 denotes the divalent aliphatic
group, the divalent aromatic group or the divalent heterocyclic
group and reference symbol R denotes the lower alkylene group.
The bifunctional organic compound C having two active
hydrogen-containing groups may include an aliphatic compound, an
aromatic compound and a heterocyclic compound. The bifunctional
organic compound C may be represented by general formula as
follows:
where reference symbol R.sup.5 denotes a divalent organic group and
symbol H is intended to mean the active hydrogen contained in the
active hydrogen-containing group. As specific examples of reference
symbol R.sup.5, there may be mentioned the active
hydrogen-containing groups enumerated hereinabove for reference
symbol R.sup.4.
The bifunctional organic compound D having two functional groups
reactable with the active hydrogen may include an aliphatic
compound, an aromatic compound and a heterocyclic compound. As the
specific examples of the bifunctional organic compounds D, there
may be mentioned those as enumerated hereinabove for the
bifunctional organic compounds B.
The preferred organo-polysiloxane derivatives according to the
present invention may be prepared by using, as raw reaction
materials, an organo-polysiloxane compound A having from 5 to 90
siloxane bonds (SiO) with active hydrogen-containing groups at both
terminals, a bifunctional aromatic epoxy compound B and a divalent
phenol compound C. As the organo-polysiloxane compound A, there may
be used a compound as represented by the general formula (6), (7)
or (8) above.
As the bifunctional aromatic epoxy compounds B, there may be
employed compounds as represented by general formula as follows:
##STR7## (where reference symbol Ar.sup.1 denotes a divalent
aromatic group; and reference symbol m denotes an integer of 1 or
2).
As the divalent phenol compounds, there may be employed compounds
as represented by general formula as follows:
(where reference symbol Ar.sup.2 denotes a divalent aromatic
group).
In the general formula (11) representing the bifunctional aromatic
epoxy compounds B, reference symbol Ar.sup.1 denotes the divalent
aromatic group. It is preferred that the reference symbol Ar.sup.1
in this case is a divalent aromatic group derived from a polycyclic
aromatic compound, particularly such as bis(phenyl)methane,
bis(phenyl)propane, bis(phenyl)ethane, naphthalene, biphenyl,
tetrabromobiphenyl and so on. The preferred bifunctional aromatic
epoxy compounds B to be employed for the present invention may be a
diglycidyl ether of a divalent phenol. As some of specific examples
thereof, there may be mentioned, for example,
bis(4-hydroxyphenyl)propane diglycidyl ether,
bis(4-hydroxy-3,5-dibromophenyl)propane diglycidyl ether,
bis(4-hydroxyphenyl)methane diglycidyl ether,
bis(4-hydroxyphenyl)ethane diglycidyl ether, resorcinol diglycidyl
ether, bis(4-hydroxy-3,5-dimethylphenyl)methane diglycidyl ether,
bis(4-hydroxy-3-methylphenyl)propane diglycidyl ether,
bis(4-hydroxyphenyl)hexafluoropropane diglycidyl ether,
2,6-naphthalenediol diglycidyl ether, tetrabromobiphenylenediol
diglycidyl ether, and so on.
In the general formula (12) representing the divalent phenol
compounds, reference symbol Ar.sup.2 denotes the divalent aromatic
group. It is preferred that the reference symbol Ar.sup.1 in this
case is a divalent aromatic group derived from the polycyclic
aromatic compounds as enumerated for reference symbol Ar.sup.1. As
some of specific examples of the divalent phenol compounds, there
may be mentioned, for example, bis(4-hydroxyphenyl)propane,
bis(4-hydroxy-3,5-dibromophenyl)propane,
bis(4-hydroxyphenyl)methane, bis(4-hydroxyphenyl)ethane,
resorcinol, bis(4-hydroxy-3,5-dimethylphenyl)methane,
bis(4-hydroxy-3-methylphenyl)propane,
bis(4-hydroxyphenyl)hexafluoropropane, 2,6-naphthalenediol,
tetrabromobiphenylenediol, and so on.
For the preparation of the organo-polysiloxane derivatives from the
raw reaction materials as described hereinabove, the first reaction
step may comprise reacting the organo-polysiloxane compound A
having from 5 to 70 siloxane bonds and having at both terminals the
active hydrogen-containing group reactable with the epoxy group
(hereinafter sometimes referred to simply as compound A) with the
bifunctional aromatic epoxy compound B (hereinafter sometimes
referred to simply as compound B). The reaction scheme in this case
may be represented by general formulas as follows, when the
compound as represented by general formula (6) above, where Z=--OH,
is employed as the compound A: ##STR8##
In the above general formulas, reference symbols R.sup.1, R.sup.2,
Ar.sup.1, m and t have the same meanings as above and reference
symbol B' denotes a group as represented by general formula as
follows: ##STR9##
The above reaction may be carried out preferably in the presence of
a catalyst such as a tetraalkyl ammonium salt such as, for example,
tetramethyl ammonium chloride, tetraethyl ammonium chloride,
tetramethyl ammonium bromide, tetramethyl ammonium iodide,
phenyltrimethyl ammonium chloride or the like. The amount of the
catalyst to be employed may range from 0.01 to 1% mole, preferably
from 0.05 to 0.1% mole, with respect to an epoxy resin. The
reaction may be carried out in a liquid state and the reaction
temperature may preferably be the temperature at which the reaction
mixture be kept in a liquid state and range usually from 80.degree.
C. to 140.degree. C., preferably from 100.degree. C. to 120.degree.
C. It is further preferred that the reaction temperature is so set
as to be elevated gradually as the reaction proceeds. Although the
reaction pressure may be ambient pressure, elevated pressure or
reduced pressure, ambient pressure is preferred. The bifunctional
aromatic epoxy compound B may preferably be employed in the amount
of 2 moles or more, preferably 2.1 moles or more, with respect to
mole of the organo-polysiloxane compound A.
Then, after the first reaction step has been finished, the reaction
is carried out by adding a mixture of the compound C with the
compound B to the resulting reaction mixture. The reaction scheme
in this case may be represented by general formulas as follows:
##STR10## In the above general formulas, reference symbols R.sup.1,
R.sup.2, Ar.sup.1, Ar.sup.2, B', m and t have the same meanings as
above and reference symbols A, B and C may be represented by
general formulas as will be described hereinbelow. Further, in the
above general formula, reference symbol n is an integer of from 1
to 14, preferably from 8 to 12, and reference symbol p is an
integer of from 1 to 17, preferably from 2 to 5: ##STR11##
The reaction may be carried out in the presence or absence of a
catalyst. Although the catalyst to be employed in this reaction may
be any one that does not promote the reaction of an alcoholic
hydroxyl group with the epoxy group to a considerable extent, the
catalysts to be employed for the first reaction step may preferably
be employed for this reaction. It can be further noted that when
the catalyst is employed in the first reaction step, it is not
particularly needed to add a catalyst in the second reaction step.
The reaction temperature may preferably be the temperature at which
the reaction mixture be kept in a liquid state and range usually
from 130.degree. C. to 170.degree. C., preferably from 140.degree.
C. to 150.degree. C. It is further preferred that the reaction
temperature is so set as to be elevated gradually as the reaction
advances. Although the reaction pressure may be ambient pressure,
elevated pressure or reduced pressure, it is preferred that the
reaction is carried out under reduced pressure or under conditions
where nitrogen gases pass.
Although the structure of the terminals of the organo-polysiloxane
derivative according to the present invention may be represented by
the structure in which the compound B or the compound C is
connected thereto (i.e. group B' or --O--Ar.sup.2 --OH), whichever
structure is to be taken is determined by the ratio of the compound
B and the compound C in the mixture and the compound which is
contained in a larger ratio is connected to the terminals thereof.
In accordance with the present invention, it is preferred that the
compound C is connected to the terminals thereof to yield the
organo-polysiloxane derivative having a phenolic hydroxyl group at
each terminal thereof.
The other preferred modes of the organo-polysiloxane derivatives
according to the present invention may be prepared by using the
organo-polysiloxane compound A having from 5 to 90 siloxane bonds
(SiO) and an active hydrogen-containing group at each terminal
thereof, a diisocyanate compound B and a glycol compound C as raw
reaction materials.
As the organo-polysiloxane compounds A, there may be employed those
as represented by the general formulas (6), (7) or (8) above.
As the diisocyanate compounds B, there may be employed those as
represented by general formula as follows:
(where reference symbol R.sup.6 denotes a divalent aromatic group
or a divalent aliphatic group).
As the glycol compounds C, there may be employed those as
represented by general formula as follows:
(where reference symbol R.sup.7 denotes a divalent aliphatic
group).
The diisocyanate compound may include an aromatic diisocyanate
compound and an aliphatic diisocyanate compound. As some of
specific examples of the diisocyanate compounds, there may be
mentioned, for example, phenylene diisocyanate, tolylene
diisocyanate, 4,4'-diphenylmethylene diisocyanate, naphthalene
diisocyanate, hexamethylene diisocyanate and so on.
As the glycol compounds, there may be mentioned, for example,
ethylene glycol, propylene glycol, butylene glycol, hexamethylene
glycol, polyethylene glycol, polypropylene glycol,
polytetramethylene glycol and so on.
For the preparation of the organo-polysiloxane derivatives from the
raw reaction materials as described hereinabove, the first reaction
step may comprise the eaction of the organo-polysiloxane compound A
with the diisocyanate compound B. The reaction scheme in this case
may be represented by general formulas as follows, when the
compound as represented by general formula (6) above, where Z=--OH,
is employed as the compound A: ##STR12##
In the above general formulas, reference symbols R.sup.1, R.sup.2,
R.sup.6, m and t have the same meanings as above and reference
symbol B' denotes a group as represented by general formula as
follows:
Then, after the first reaction step has been finished, the reaction
is carried out by adding a mixture of the compound C with the
compound B to the resulting reaction mixture. The reaction scheme
in this case may be represented by general formulas as follows:
##STR13## In the above general formulas, reference symbols R.sup.1,
R.sup.2, R.sup.6, R.sup.7, B', m and t have the same meanings as
above and reference symbols A, B and C may be represented by the
following general formulas. Further, in the above general formulas,
reference symbol n denotes an integer of from 1 to 14, preferably
from 8 to 12, and reference symbol p denotes an integer of from 1
to 17, preferably from 2 to 5: ##STR14##
The other preferred modes of the organo-polysiloxane derivatives
according to the present invention may be prepared by using the
organo-polysiloxane compound A having from 5 to 90 siloxane bonds
(SiO) and an active hydrogen-containing group at each terminal
thereof, a dicarboxylic acid compound B and a diamino compound C as
raw reaction materials.
As the organo-polysiloxane compounds A, there may be mployed those
as represented by the general formulas (6), (7) r (8) above.
As the dicarboxylic acid compounds B, there may be employed those
as represented by general formula as follows:
(where reference symbol R8 denotes a divalent aromatic group or
divalent aliphatic group; and reference symbol M is OH or halogen
atom).
As the diamino compounds C, there may be employed those as
represented by general formula as follows:
(where reference symbol R.sup.9 denotes a divalent aromatic group
or a divalent aliphatic group).
As the dicarboxylic acid compounds B, there may be mentioned, for
example, terephathalic acid, naphthalene dicarboxylic acid, maleic
acid, succinic acid, adipic acid, sebacic acid and so on.
As the diamino compounds C, there may be mentioned, for example,
phenylene diamine, tolylene diamine, butylene diamine,
hexamethylene diamine and so on.
For the preparation of the organo-polysiloxane derivatives from the
raw reaction materials as described hereinabove, the first reaction
step may comprise the reaction of the organo-polysiloxane compound
A with the dicarboxylic acid compound B. The reaction scheme in
this case may be represented by general formulas as follows, when
the compound as represented by general formula (6) above, where
Z=--NH.sub.2, is employed as the compound A: ##STR15##
In the above general formulas, reference symbols R.sup.1, R.sup.2,
R.sup.8, M, m and t have the same meanings as above and reference
symbol B denotes a group as represented by general formula as
follows:
Then, after the first reaction step has been finished, the reaction
is carried out by adding a mixture of the compound C with the
compound B to the resulting reaction mixture. The reaction scheme
in this case may be represented by general formulas as follows:
##STR16## In the above general formulas, reference symbols R.sup.1,
R.sup.2, R.sup.3, R.sup.9, M, B', m and t have the same meanings as
above and reference symbols A, B and C may be represented by the
following general formulas. Further, in the above general formulas,
reference symbol n denotes an integer of from 1 to 14, preferably
from 8 to 12, and reference symbol p denotes an integer of from 1
to 17, preferably from 2 to 5: ##STR17##
The other preferred modes of the organo-polysiloxane derivatives
according to the present invention may be prepared by using the
organo-polysiloxane compound A having from 5 to 90 siloxane bonds
(SiO) and an active hydrogen-containing group at each terminal
thereof, a carbonic acid diester compound B and a dihydroxy
compound C as raw reaction materials.
As the organo-polysiloxane compounds A, there may be employed those
as represented by the general formulas (6), (7) or (8) above.
As the carbonic acid diester compounds B, there may be employed
those as represented by general formula as follows: ##STR18##
(where reference symbol R.sup.10 denotes an aliphatic group or an
aromatic group).
As the dihydroxy compounds C, there may be employed those as
represented by general formula as follows:
(where reference symbol R.sup.11 denotes a divalent aliphatic group
or a divalent aromatic group).
As the carbonic acid diester compounds B, there may be mentioned,
for example, dimethyl carbonate, diethyl carbonate, diphenyl
carbonate, ditolyl carbonate, and so on.
As the dihydroxy compounds C, there may be mentioned, for example,
ethylene glycol, propylene glycol, butylene glycol, catechol,
bisphenol A, and so on.
For the preparation of the organo-polysiloxane derivatives from the
raw reaction materials as described hereinabove, the first reaction
step may comprise the reaction of the organo-polysiloxane compound
A with the dicarbonic acid diester compound B. The reaction scheme
in this case may be represented by general formulas as follows,
when the compound as represented by general formula (6) above,
where Z=--OH, is employed as the compound A: ##STR19##
In the above general formulas, reference symbols R.sup.1, R.sup.2,
R.sup.10, m and t have the same meanings as above and reference
symbol B' denotes a group as represented by general formula as
follows: ##STR20##
Then, after the first reaction step has been finished, the reaction
is carried out by adding a mixture of the compound C with the
compound B to the resulting reaction mixture. The reaction scheme
in this case may be represented by general formulas as follows:
##STR21##
In the above general formulas, reference symbols R.sup.1, R.sup.2,
R.sup.10, R.sup.11, B', m and t have the same meanings as above and
reference symbols A, B and C may be represented by the following
general formulas. Further, in the above general formulas, reference
symbol n denotes an integer of from 1 to 14, preferably from 8 to
12, and reference symbol p denotes an integer of from 1 to 17,
preferably from 2 to 5: ##STR22##
The other preferred modes of the organo-polysiloxane derivatives
according to the present invention may be prepared by using the
organo-polysiloxane compound A having from 5 to 90 siloxane bonds
(SiO) and an active hydrogen-containing group at each terminal
thereof, a dicarboxylic acid diester compound B and a dihydroxy
compound C as raw reaction materials.
As the organo-polysiloxane compounds A, there may be employed those
as represented by the general formulas (6), (7) or (8) above.
As the dicarboxylic acid diester compounds B, there may be employed
those as represented by general formula as follows:
(where reference symbol R.sup.12 denotes a divalent aliphatic group
or a divalent aromatic group; and reference symbol R.sup.13 denotes
a lower alkyl group).
As the dihydroxy compounds C, there may be employed those as
represented by general formula as follows:
(where reference symbol R.sup.11 denotes a divalent aliphatic group
or a divalent aromatic group).
As the dicarboxylic acid diester compounds B, there may be
mentioned, for example, dimethyl malonate, diethyl malonate,
dimethyl adipate, dimethyl sebacate, dimethyl terephathalate,
diethyl terephathalate, and so on.
As the dihydroxy compounds C, there may be mentioned, for example,
ethylene glycol, propylene glycol, butylene glycol, catechol,
bisphenol A, and so on.
For the preparation of the organo-polysiloxane derivatives from the
reaction materials as described hereinabove, the first reaction
step may comprise the reaction of the organo-polysiloxane compound
A with the dicarbonic acid diester compound B. The reaction scheme
in this case may be represented by general formulas as follows,
when the compound as represented by general formula (6) above,
where Z=--OH, is employed as the compound A: ##STR23##
In the above general formulas, reference symbols R.sup.1, R.sup.2,
R.sup.12, R.sup.13, m and t have the same meanings as above and
reference symbol B' denotes a group as represented by general
formula as follows:
Then, after the first reaction step has been finished, the reaction
is carried out by adding a mixture of the compound C with the
compound B to the resulting reaction mixture. The reaction scheme
in this case may be represented by general formulas as follows:
##STR24##
In the above general formulas, reference symbols R.sup.1, R.sup.2,
R.sup.12, R.sup.13, R.sup.14, B', m and t have the same meanings as
above and reference symbols A, B and C may be represented by the
following general formulas. Further, in the above general formulas,
reference symbol n denotes an integer of from 1 to 14, preferably
from 8 to 12, and reference symbol p denotes an integer of from 1
to 17, preferably from 2 to 5: ##STR25##
In accordance with the present invention, the organo-polysiloxane
derivative having the structure as represented by general formula
(1) in its moiety (hereinafter referred to sometimes as compound S)
is characterized in that the moiety contains a long organo-siloxane
chain and a long aromatic ring-containing chain or a long aliphatic
chain, and it demonstrates excellent properties as a dispersing
agent for dispersing a silicone gel homogeneously in a curable
resin.
The internal stress of a cured product prepared by curing a curable
resin composition with the silicone gel and the compound S
dispersed homogeneously in the curable resin becomes very low due
to the action of the silicone gel dispersed homogeneously in the
cured product.
The silicone gel to be used for the present invention is known to
the art and it is also known that such silicone gel can be prepared
by condensation reaction method or addition reaction method. The
silicone gel to be employed for the curable resin composition
according to the present invention can be prepared by each of the
methods.
The silicone gel has a polysiloxane structure and it can be
prepared, for example, by reacting a vinyl group-containing
organo-polysiloxane with SiH group at the rate of 0.3 group of the
former to 0.8 group of the latter in the presence of a
platinum-type compound as a catalyst. The processes of the
preparation of the silicone gel are described in more detail, for
example, in Japanese Patent Unexamined Publication Nos. 54-48,720,
48-17,847 and 45-9,476.
The rate of the silicone gel to the curable resin may range from 1
to 100 parts by weight, preferably from 5 to 50 parts by weight,
with respect to 100 parts by weight of the curable resin. It is
preferred that the silicone gel is in a form of fine particles
having a particle size of 1 mm or smaller, preferably 200 .mu.m or
smaller, more preferably ranging from 2 to 0.5 .mu.m. The methods
for addition of the silicone gel to the curable resin may include,
for example, the method comprising adding the silicone gel in a
powdery form to a liquid curable resin and dispersing the former in
the latter, the method comprising adding a homogeneous mixture of
the silicone gel with a curable resin such as an epoxy resin or the
like to the curable resin, and the method comprising carrying out
the reaction for the formation of the silicone gel in the curable
resin. The compositions having the silicone gel formulated with the
curable resin are described in more detail, for example, in
Japanese Patent Unexamined Publication No. 61-185,527.
The curable resin may include a thermosetting resin and a
photosetting resin. As such resins, there may be mentioned,
forexample, an epoxy resin, an unsaturated polyester resin, a
cyanate ester resin, a melamine resin, a urea resin, a phenol
resin, a urethane resin, a diallylphthalate resin, a BT
(bismaleimide/triazine resin), and so on. Among the resins as
described hereinabove, the epoxy resin is employed most frequently
in electrical and electronic field. A detailed description will be
made of the epoxy resin.
As the epoxy resin, there may be employed any one having two epoxy
groups or more in its moiety and a variety of known epoxy resins in
a liquid form or a solid form at ambient temperature may be
employed for the present nvention. As the epoxy resins, there may
be mentioned, for example, a bisphenol A type epoxy resin, a
bisphenol F type epoxy resin, a bisphenol AD type epoxy resin, a
bisphenol S type epoxy resin, an alicyclic type epoxy resin, a
glycidyl ester type epoxy resin, a glycidyl amine type epoxy resin,
a hetero-cyclic type epoxy resin, a polyolefinic type epoxy resin,
an iodided type epoxy resin, a tetrahydroxyphenylethane epoxy
resin, a phenol novolak type epoxy resin, a cresol novolak type
epoxy resin, a dihydroxynaphthalene type epoxy resin, a silicone
denatured type epoxy resin, and so on.
The compound S may be formulated with the epoxy resin at the rate
of from 10 to 100 parts by weight, preferably from 30 to 50 parts
by weight, with respect to 100 parts by weight of the epoxy resin.
Further, the rate of the compound S with respect to the silicone
gel may range from 10 to 50 parts by weight, preferably from 15 to
30 parts by weight, with respect to 100 parts by weight of the
silicone gel.
The epoxy resin composition with the silicone gel and the compound
S formulated with the epoxy resin can be cured with a curing agent,
thereby yielding a curable composition.
As the curing agent to be employed for the present invention, there
may be employed a variety of known curing agents. The such curing
agents may include, for example, an amine type curing agent, an
acid anhydride type curing agent, an imidazole type curing agent, a
polyamide type curing agent, a phenol resin type curing agent, a
polyvinylphenol type curing agent, a latent curing agent such as a
boron trifluoride amine complex type curing agent, a dicyane
diamide type curing agent,an organic acid hydrazide type curing
agent, a diaminomaleonitrile type curing agent, a melamine type
curing agent, an amide imide type curing agent, a polyamine salt
type curing agent, a molecular sieve type curing agent, a
ultraviolet curing agent (such as an aromatic diazonium salt, a
diallyl iodium salt, a triaryl sulfonium salt, a triaryl cerenium
salt and so on), a photosetting agent (such as a polymercaptane, a
polysulfide resin). These curing agents are described in more
detail, for example, in literature such as New Epoxy Resins, pp.
164-254, published by KK Shokoudo (Japan).
Among the curing agents as described hereinabove, particularly the
amine type curing agent and the acid anhydride type curing agent
can be employed preferably. As the amine type curing agents, there
may be mentioned, for example, an aliphatic polyamine such as
diethylene triamine, triethylene tetraamine, tetraethylene
pentamine, diethylaminopropyl amine and so on; an alicyclic
polyamine such as mencene diamine, isophorone diamine,
N-aminoethylpiperazine, bis(4-amino-3-thylcyclohexyl)methane,
bis(4-aminocyclohexyl)methane and so on; an aromatic polyamine such
as methaxylene diamine, diaminodiphenylmethane,
diaminodiphenylsulfone, methaphenylenediamine and so on; a
polyamidopolyamine, a dicyane diamide, adipic acid dihydrazide, and
so on. As the acid anhydride curing agents, there may be mentioned,
for example, a monofunctional acid anhydride such as phthalic
anhydride, tetrahydrophthalic anhydride, hexahydrophthalic
anhydride, methyltetrahydrophthalic anhydride,
methylhexahydrophthalic anhydride, methylnadic anhydride, dodecyl
succinic anhydride, succinic anhydride, chlorendic anhydride and so
on; a bifunctional acid anhydride such as pyromellitic anhydride,
benzophenone tetracarboxylic anhydride, ethylene glycol
bis(anhydrotrimate), methylcyclohexene tetracarboxylic anhydride
and so on; and an acid anhydride containing a free carboxyl group
such as trimellitic anhydride, polyazelaic anhydride and so on.
Generally, together with the acid anhydride type curing agents, a
basic cure acceleration agent is used. As the basic cure
acceleration agents, there may be mentioned, for example, an
aliphatic amine such as tetratrialkylamine, tetramethylguanidine,
triethanol amine and so on; an licyclic amine such as piperidine,
N,N'-dimethylpiperazine, triethylene diamine and so on; a
heterocyclic amine such as pyridine, picoline,
1,8-diazabicyclo[5.4.0]-7-undecene and so on; and an aromatic amine
such as benzyldimethyl amine, 2-(dimethylaminomethyl)phenol,
2,4,6-tris(diaminometyl)phenol and so on.
The epoxy resin compositions may be formulated with an accessory
ingredient customarily used for conventional epoxy resin
compositions, such as a cure accelerator, a curing catalyst, a
filler, a fire retardant, a coupling agent, a diluent, a coloring
agent, a laser masking agent or the like.
The epoxy resin compositions according to the present invention may
be in a liquid or powdery form and cured at ambient temperature or
at elevated temperature.
As the organo-polysiloxane derivative according to the present
invention contains both of the organo-polysiloxane chain and the
aromatic ring-containing chain or the long aliphatic chain, it can
advantageously be employed as a dispersing agent for homogeneously
dispersing the silicone gel in the curable resin. In other words,
as the organo-polysiloxane derivative according to the present
invention has the polysiloxane chain having compatibility with the
silicone gel and the aromatic ring-containing chain or the
aliphatic chain having compatibility with the curable resin, the
curable resin composition with the silicone gel homogeneously
dispersed therein can be obtained by stirring and mixing the
silicone gel with the curable resin in a liquid state, together
with the organo-polysiloxane derivative according to the present
invention.
The curable resin compositions according to the present invention,
containing the silicone gel and the organo-polysiloxane derivative,
can provide a cured product having a very low internal stress, when
they are cured. The curable resin composition according to the
present invention can be applied, particularly as a sealing
material for electrical and electronic parts, by taking advantage
of its very low internal stress of its cured product.
The curable resin compositions containing the silicone gel and the
organo-polysiloxane derivatives according to the present invention
may be cured into a cured product having a very low degree of
internal stress. The curable resin compositions according to the
present invention can advantageously be applied particularly as a
sealing material for electrical and electronic parts by taking
advantage of the very low degrees of internal stress in their cured
products.
Although the curable resin composition according to the present
invention may be a composition in a liquid state at ambient
temperature, it may also be in a powdery state at ambient
temperature. For the preparation of the composition in the powdery
state at ambient temperature, the curable resin in a powdery state
is molten to yield a molten liquid to which in turn the silicone
gel and the organo-polysiloxane derivative according to the present
invention are added and which is then mixed, followed by cooling
the resulting mixture and allowing it to solidify, and the
solidified material was pulverized into powders.
The curable resin compositions according to the present invention
can be employed favorably as adhesive, paint, insulating materials
for electrical and electronic parts, sealing materials for
electrical and electronic parts, and molding materials, like
conventional curable resin compositions .
BRIEF DESCRIPTION OF THE DRAWINGS
FIG. 1 is a plan view showing a specimen for use in measurement of
an internal stress of a cured product by means of steel ring
method.
FIG. 2 is a sectional view taken along A--A' line of FIG. 1.
In FIGS. 1 and 2, reference numeral 1 denotes a cured resin
product, reference numeral 2 a steel ring, and reference numeral 3
a strain gauge connection line.
EXAMPLES
A more detailed description will be made of the present invention
by way of examples.
Example 1
(Synthesis of dispersing agent A)
Into a flask with a stirrer mounted thereon were placed 100.0 grams
of phenol-terminal silicone oil BY16-752 (molecular weight=3,148;
number of siloxane bonds t=39; product of Toray-Dow Corning
Silicone K.K.), 28.70 grams of bisphenol A diglycidyl ether
EXA-850CRP (epoxy equivalent=171; product of Dai-Nippon Ink K.K.),
and 0.03 gram of tetramethylammonium chloride as a catalyst, and
the mixture was stirred on an oil bath at 100.degree. C. for 5
hours, then at 120.degree. C. for 4 hours and further at
130.degree. C. for 1 hour in order to proceed with reaction. Then,
the stirring was stopped, and 71.3 grams of a mixture pre-prepared
by dissolving bisphenol A (molecular weight=228) in the equivalent
amount of bisphenol A diglycidyl ether EXA-850CRP was added to the
flask, followed by stirring at 130.degree. C. for another 1 hour.
Thereafter, the pressure within the flask is reduced, followed by
stirring at 140.degree. C. for 1 hour and then at 150.degree. C.
for another 1 hour, thereby yielding an objective material which
were referred to herein as dispersing agent A.
The dispersing agent A was an oily material that was in a liquid
state at ambient temperature and that demonstrated a viscosity of
20,000 poises at 25.degree. C. In the dispersing agent A, an
average polymerization degree of the bisphenol A diglycidyl ether
and the bisphenol A was 4.9 and the weight-average molecular weight
was 31,000. It is confirmed by the proton NMR that the dispersing
agent A had a polyether structure and an epoxy group at one or both
of its terminals.
Example 2
(Synthesis of dispersing agent B)
Into a flask with a stirrer mounted thereon were placed 100.0 grams
of phenol-terminal silicone oil BY16-752, 19.0 grams of naphthalene
bone-type diglycidyl ether HP-4032D (epoxy equivalent=142; product
of Dai-Nippon Ink K.K.), and 0.03 gram of tetramethylammonium
chloride as a catalyst, and the mixture was stirred on an oil bath
at 100.degree. C. for 5 hours, then at 120.degree. C. for 4 hours
and further at 130.degree. C. for 1 hour in order to proceed with
reaction. Then, the stirring was stopped, and 81.0 grams of a
mixture pre-prepared by dissolving bisphenol A in the equivalent
amount of bisphenol A diglycidyl ether HP-4032D was added to the
flask, followed by stirring at 130.degree. C. for another 1 hour.
Thereafter, the pressure within the flask is reduced, followed by
stirring at 140.degree. C. for 1 hour and then at 150.degree. C.
for another 1 hour, thereby yielding an objective material which
were referred to herein as dispersing agent B.
The dispersing agent B was an oily material that was in a liquid
state at ambient temperature and that demonstrated a viscosity of
12,000 poises at 25.degree. C. In the dispersing agent B., an
average polymerization degree of the bisphenol A diglycidyl ether
and the bisphenol A was 5.6 and the weight-average molecular weight
was 25,000. It is confirmed by the proton NMR that the dispersing
agent B had a polyether structure and an epoxy group at one or both
of its terminals.
Reference Example 1
(Method for dispersing silicone gel into epoxy resin)
In a flask equipped with a high-speed stirrer were placed 120.0
grams of an epoxy resin as a base and 40.0 grams of the dispersing
agent A or B prepared above, and the mixture was stirred at a high
speed for about 1 hour at 100.degree. C. on an oil bath. Then,
100.0 grams of a formulation TSE3062A (product of Toshiba Silicone
K.K.) consisting of a vinyl group-containing silicone and a Pt type
catalyst was added to the mixture, and the resulting mixture was
allowed to let the silicone dispersed in the resin gel while
stirring at a high speed. The stirring continued for about 3 hours,
thereby completing the gelling thoroughly to yield a silicone
gel-dispersed type epoxy resin.
Example 3
In accordance with Reference Example 1, there were employed
bisphenol A type epoxy resin RE-310S (product of Nippon Kayaku
K.K.) as the epoxy resin acting as the base and the dispersing
agent A as the dispersing agent, thereby yielding a silicone
gel-dispersed type epoxy resin. With 100 parts by weight of the
resulting silicone gel-dispersed type epoxy resin were mixed 30
parts by weight of methylhexahydrophthalic anhydride HN5500
(product of Hitachi Kasei K.K.) as a curing agent and 1 part by
weight of benzylmethylamine (BDMA) as a cure accelerating agent
thereby yielding an epoxy resin formulation. Table 1 below shows
characteristics of a cured material obtained by curing the
resulting epoxy resin formulation.
Example 4
In accordance with Reference Example 1, there were employed
bisphenol F type epoxy resin EPC-830LVP (product of Dai-Nippon Ink
K.K.) as the epoxy resin acting as the base and the dispersing
agent A as the dispersing agent, thereby yielding a silicone
gel-dispersed type epoxy resin. With 100 parts by weight of the
resulting silicone gel-dispersed type epoxy resin were mixed 33
parts by weight of the HN5500 as a curing agent and 1 part by
weight of the BDMA as a cure accelerating agent thereby yielding an
epoxy resin formulation. Table 1 below shows characteristics of a
cured material obtained by curing the resulting epoxy resin
formulation.
Example 5
There were employed naphthalene-bone type epoxy resin HP-4032D
(product of Dai-Nippon Ink K.K.) as the epoxy resin acting as the
base and the dispersing agent B as the dispersing agent, thereby
yielding a silicone gel-dispersed type epoxy resin. With 100 parts
by weight of the resulting silicone gel-dispersed type epoxy resin
were mixed 39 parts by weight of the HN5500 and 1 part by weight of
the BDMA, thereby yielding an epoxy resin formulation. Table 1
below shows characteristics of a cured material obtained by curing
the resulting epoxy resin formulation.
Example 6
In accordance with Reference Example 1, there were employed
alicyclic epoxy resin CY179 (product of Ciba-Geigy K.K.) as the
epoxy resin acting as the base and the dispersing agent B as the
dispersing agent, thereby yielding a silicone gel-dispersed type
epoxy resin. With 100 parts by weight of the resulting silicone
gel-dispersed type epoxy resin were mixed 40 parts by weight of the
HN5500 and 1 part by weight of the BDMA, thereby yielding an epoxy
resin formulation. Table 1 below shows the characteristics of a
cured material obtained by curing the resulting epoxy resin
formulation.
Example 7
There were employed trifunctional glycidyl amine ELM-100 (product
of Sumitomo Kagaku Kogyo K.K.) as the epoxy resin acting as the
base and the dispersing agent B as the dispersing agent, thereby
yielding a silicone gel-dispersed type epoxy resin. With 100 parts
by weight of the resulting silicone gel-dispersed type epoxy resin
were mixed 52 parts by weight of the HN5500 and 1 part by weight of
the BDMA, thereby yielding an epoxy resin formulation. Table 1
below shows characteristics of a cured material obtained by curing
the resulting epoxy resin formulation.
Comparative Example 1
There were employed EPC-830LVP as the epoxy resin acting as the
base and commercially available polyether denatured silicone
TSF4452 (product of Toshiba Silicone K.K) as the dispersing agent,
thereby yielding a silicone gel-dispersed type epoxy resin. With
100 parts by weight of the resulting silicone gel-dispersed type
epoxy resin were mixed 33 parts by weight of the HN5500 and 1 part
by weight of the BDMA, thereby yielding an epoxy resin formulation.
Table 2 below shows characteristics of a cured material obtained by
curing the resulting epoxy resin formulation.
Comparative Example 2
In accordance with Reference Example 1, trials have been made to
yield a silicone gel-dispersed type epoxy resin by using an
epoxy/silicone adduct compound as a dispersing agent, which was
prepared by reacting phenol-terminal silicone oil BY16-752 with
EXA-850CRP at the rate of one molecule of the former to two
molecules of the latter, and EPC-830LVP as the epoxy resin acting
as the base. However, the silicone gel was separated gradually from
the resinous ingredient during allowing the reaction mixture to
stand after the stirring was stopped. Accordingly, the evaluation
of characteristics of the formulation has been terminated.
Comparative Example 3
According to Reference Example 1, trials have been made to yield a
silicone gel-dispersed type epoxy resin by using EPC-830LVP as the
epoxy resin acting as a base without using any dispersing agent;
however, the trials have been stopped because the silicone gel was
separated from the resinous ingredient immediately. Accordingly,
the evaluation of characteristics of the resulting product has been
terminated.
Comparative Example 4
An epoxy resin formulation was prepared by mixing 104 parts by
weight of the HN5500 and 1 part by weight of the BDMA per 100 parts
by weight of an epoxy resin HP-4032D. Table 3 shows the
characteristics of a cured material obtained by curing the
resulting epoxy resin formulation.
Comparative Example 5
An epoxy resin formulation was prepared by mixing 118 parts by
weight of the HN5500 and 1 part by weight of the BDMA with respect
to 100 parts by weight of an epoxy resin HP-4032D. Table 3 shows
the characteristics of a cured material obtained by curing the
resulting epoxy resin formulation.
Comparative Example 6
An epoxy resin formulation was prepared by mixing 95 parts by
weight of the HN5500 and 1 part by weight of the BDMA with respect
to 100 parts by weight of commercially available silicone-denatured
resin A-20NCL (product of Nippon Yushi K.K.) containing a
naphthalene-bone type epoxy resin as a base. Table 3 shows the
characteristics of a cured material obtained by curing the
resulting epoxy resin formulation.
Comparative Example 7
An epoxy resin formulation was prepared by mixing 80 parts by
weight of HP-4032D, 14 parts by weight of epoxy group-containing
silicone oil FZ3720 (Nihon Uniker K.K.), 6 parts by weight of epoxy
group-containing polyether denatured silicone oil FZ3736 (Nihon
Uniker K.K.), 97 parts by weight of the HN5500 and 1 part by weight
of the BDMA. Table 3 shows the characteristics of a cured material
obtained by curing the resulting epoxy resin formulation.
Comparative Example 8
An epoxy resin formulation was prepared by mixing 100 parts by
weight of commercially available silicone-denatured resin EPC-40NCL
(Nippon Yushi K.K.) containing bisphenol F type epoxy resin as a
base with 83 parts by weight of the HN5500 and 1 part by weight of
the BDMA. Table 3 shows the characteristics of a cured material
obtained by curing the resulting epoxy resin formulation.
(Method of Evaluation)
The epoxy resin formulation was cured at 100.degree. C. for 1 hour
and then at 180.degree. C. for another 1 hour, thereby yielding a
cured product that in turn was subjected to evaluation for its
characteristics as follows:
(Tg): Measured by the DSC method and Tg was employed as a parameter
for thermal resistance.
(Internal stress): A steel was embedded in a cured resin material
and a stress to be caused to occur in the cured resin material was
measured by the steel ring method*. In a table, the values of the
internal stress are shown when measured at -70.degree. C.
*Steel ring method
As shown in FIG. 1, a test specimen was prepared by embedding a
steel ring in the center of a cured resin material and it was
tested by lowering its temperature from 180.degree. C. to
-70.degree. C. at the rate of 1 C per minute. The amount of
deflection of the steel ring caused to occur by the shrinkage
stress of the cured resin material during the decrease in the
temperature was read at each of the temperatures with a strain
gauge stuck inside the steel ring embedded therein. The internal
stress was given as a stress value .sigma. at an optional
temperature by inserting the read amount into the following
equation:
where E is a Young ratio of the steel;
d is a thickness of the steel ring;
r is an inner radius of the steel ring; and is an amount of
circumferential deflection of the steel ring.
(Resistance to moisture)
A cured resin material formed in a 50 mm.times.50 mm.times.2 mm
shape was processed with a pressure cooker test (PCT) (100 hours,
121.degree. C., 2 atmospheric pressure, saturation test) and then
tested for dielectric constant at room temperature and 10 KHz,
dielectric dissipation factor, and volume specific resistance at
500 V. These characteristics after the moisture processing were
used as parameters to moisture resistance.
Further, a water absorption ratio was given by a variation in the
weight of the test specimen before and after the pressure cooker
test.
TABLE 1
__________________________________________________________________________
EXAMPLES 3 4 5 6 7
__________________________________________________________________________
SILICONE GEL- DISPERSED TYPE EPOXY RESIN (PARTS/WEIGHT) BASE RESIN
RE-310S EPC-830LVP HP-4032D CY179 ELM-100 120 120 120 120 120
DISPERSING AGENT A 40 A 40 B 40 B 40 B 40 SILICONE GEL TSE3062
TSE3062 TSE3062 TSE3062 TSE3062 200 200 200 200 200 FORMULATION FOR
EVALUATION OF PROPERTIES (PARTS/WEIGHT) RESIN ABOVE RESIN ABOVE
RESIN ABOVE RESIN ABOVE RESIN ABOVE RESIN 100 100 100 100 100
CURING AGENT HN5500 HN5500 HN5500 HN5500 HN5500 30 33 39 40 52 CURE
ACCELERATOR BDMA BDNA BDMA BDMA BDMA 1 1 1 1 1 PROPERTIES OF CURED
MATERIAL Tg (.degree.C.) 150 140 160 180 190 INTERNAL STRESS AT
-70.degree. C. 0.33 0.25 0.24 0.77 0.45 (kg/square mm) PROPERTIES
AFTER PROCESSING BY PCT FOR 100 h DIELECTRIC 3.1 3.3 3.2 3.7 NOT
MEASURED CONSTANT (10 KHz) DIELECTRIC 0.009 0.010 0.008 0.015 NOT
MEASURED DISSIPATION FACTOR (10 KHz) VOLUME-SPECIFIC 5.1 .times.
10.sup.14 4.8 .times. 10.sup.14 1.2..times. 10.sup.15 2.3 .times.
10.sup.14 NOT MEASURED RESISTANCE (.OMEGA.-cm, 500 V) WATER
ABSORPTION 1.64 1.72 1.36 4.83 NOT MEASURED RATIO (%)
__________________________________________________________________________
NOTES: CURING CONDITIONS 100.degree. C./1 H + 180.degree. C./1
H
TABLE 2
__________________________________________________________________________
COMPARATIVE EXAMPLES 1 2 3
__________________________________________________________________________
SILICONE GEL- DISPERSED TYPE EPOXY RESIN (PARTS/WEIGHT) BASE RESIN
EPC-830LVP 120 EPC-830LVP 120 EPC-820LV 120 DISPERSING AGENT
TSF4452 40 EPOXY/SILICONE 40 NONE ADDUCT SILICONE GEL TSE3062 200
TSE3062 200 TSE3062 200 FORMULATION FOR EVALUATION OF PROPERTIES
(PARTS/WEIGHT) RESIN ABOVE RESIN 100 -- -- CURING AGENT HN550 33 --
-- CURE ACCELERATOR BDMA 1 -- -- PROPERTIES OF CURED MATERIAL Tg
(.degree.C.) 140 SUSPENDED SUSPENDED INTERNAL STRESS AT -70.degree.
C. 0.24 DUE TO DUE TO (kg/square mm) SEPARATION SEPARATION
PROPERTIES AFTER OF SILICONE OF SILICONE PROCESSING BY GEL FROM GEL
FROM PCT 100 h RESIN RESIN DIELECTRIC COULD NOT BE CONSTANT (10
KHz) MEASURED DIELECTRIC COULD NOT BE DIS-SIPATION FACTOR MEASURED
(10 KHz) VOLUME-SPECIFIC <1 .times. 10.sup.9 RESISTANCE
(.OMEGA.-cm, 500 V) WATER ABSORPTION ELUTED RATIO (%)
__________________________________________________________________________
NOTES: CURING CONDITIONS 100.degree. C./1 H + 180.degree. C./1
H
TABLE 3
__________________________________________________________________________
COMPARATIVE EXAMPLES 4 5 6 7 8
__________________________________________________________________________
FORMULATION FOR EVALUATION OF PROPERTIES (PARTS/WEIGHT) RESIN
EPC-830LVP HP-4032D A-20NCL EPOXY COMP* EPC-40NCL 100 100 100 100
100 CURING AGENT HN5500 HN5500 HN5500 HN5500 HN5500 104 118 95 97
63 CURE ACCELERATOR BDMA BDNA BDMA BDMA BDMA 1 1 1 1 1 PROPERTIES
OF CURED MATERIAL Tg (.degree.C.) 140 160 155 150 135 INTERNAL
STRESS AT -70.degree. C. 1.39 1.52 1.26 1.10 0.82 (kg/square mm)
PROPERTIES AFTER PROCESSING BY PCT 100 h DIELECTRIC 3.3 3.4 3.6 3.7
COULD NOT BE CONSTANT (10 KHz) MEASURED DIELECTRIC 0.011 0.013
0.031 0.038 COULD NOT BE DISSIPATION FACTOR MEASURED (10 KHz)
VOLUME-SPECIFIC 3.4 .times. 10.sup.15 2.3 .times. 10.sup.15 1.3
.times. 10.sup.15 1.3 .times. 10.sup.15 5.2 .times. 10.sup.9
RESISTANCE (.OMEGA.-cm, 500 V) WATER ABSORPTION 1.02 1.24 1.49 1.53
ELUTED RATIO (%)
__________________________________________________________________________
NOTES: CURING CONDITIONS: 100.degree. C./1 H + 180.degree. C./1 H
COMP*: HP4032D/80 PARTS BY WEIGHT + FZ3720/14 PARTS + FZ3736/6
PARTS (FZ3720: NIPPON UNIKER K.K.: EPOXY DENATURED SILICONE OIL)
(FZ3736: NIPPON UNIKER K.K.: EPOXYPOLYETHER DENATURED SILICONE
OIL)
Example 8
A mixture of 1 part by weight of an organic peroxide type curing
agent of an unsaturated polyester resin (trade name "Permeric N";
prepared by Nihon Yushi K.K.), 50 parts by weight of the silicone
gel-dispersed type epoxy resin prepared in Example 3, 351 parts by
weight of molten silica, 2.2 parts by weight of a vinyl
group-containing silane coupling agent (trade name "S210"; prepared
by Chisso K.K.) and 1 part by weight of benzyldimethylamine (an
agent for curing an epoxy resin) was formulated with an unsaturated
polyester resin (trade name "Polylight TE-100"; prepared by
Dai-Nippon Ink K.K.), and the resulting formulation was heated at
60.degree. C. for 1 hour and further at 100.degree. C. for another
1 hour, thereby curing the formulation. It was found that the
resulting cured formulation gave an internal stress as low as 0.28
kg/mm.sup.2 at -50.degree. C.
Example 9
A mixture of 0.14 part by weight of manganese octylate (a curing
agent for a cyanate ester resin), 50 parts by weight of the
silicone gel-dispersed type epoxy resin prepared in Example 3, 251
parts by weight of molten silica and 2.2 parts by weight of a vinyl
group-containing silane coupling agent (trade name "A-187";
prepared by Nippon Uniker K.K.) was formulated with 100 parts by
weight of a cyanate ester resin (trade name "Arocy L-10"; prepared
by Asahi Chiba K.K.), and the resulting formulation was heated at
100.degree. C. for 1 hour and further at 130.degree. C. for another
1 hour, followed by heating at 180.degree. C. for 3 hours, thereby
curing the formulation. It was found that the resulting cured
formulation gave an internal stress as low as 0.4 kg/mm.sup.2 at
-40.degree. C.
Example 10
(Synthesis of Dispersing Agent C)
In a flask equipped with a stirrer mounted thereon were placed
100.0 grams of silicone oil BY-752 having phenol groups at its
terminals and 15.9 grams of 4,4'-diphenylmethane diisocyanate
(MDI), and the mixture was reacted by stirring it for 5 hours at
60.degree. C. on an oil bath. After the stirring was stopped, 22.0
grams of propylene glycol (PG) and 62.6 grams of MDI were added to
the mixture in the flask, and the resulting mixture was stirred at
60.degree. C. for 5 hours, followed by reducing the pressure within
the flask and then stirring the mixture at 80.degree. C. for 1
hour, thereby yielding an objective material referred to herein as
dispersing agent C.
The dispersing agent C was an oily material that was in a liquid
state at ambient temperature and that demonstrated a viscosity of
10,000 poises at 25.degree. C. In the dispersing agent C, a
polymerization degree was 9.2 and the weight-average molecular
weight was 20,000. It is confirmed by the proton NMR that the
dispersing agent C had a polyurethane structure and an OH group at
one or both of its terminals.
Example 11
(Method for dispersing silicone gel into epoxy resin)
In a flask equipped with a high-speed stirrer mounted thereon were
placed 120.0 grams of an epoxy resin as a base and 40.0 grams of
the dispersing agent C prepared above, and the mixture was stirred
at a high speed for about 1 hour at 80.degree. C. on an oil bath.
Then, 100.0 grams of a formulation "TSE3062A" (prepared by Toshiba
Silicone K.K.) consisting of a vinyl group-containing silicone and
a Pt type catalyst was added to the mixture, and the resulting
mixture was allowed to let the silicone dispersed in the resin gel
while stirring at a high speed. The stirring was continued for
about 3 hours, thereby completing the gelling thoroughly to yield a
silicone gel-dispersed type epoxy resin. It was confirmed that the
silicone gel was homogeneously dispersed in the epoxy resin by the
action of the dispersing agent C.
* * * * *